Condensation product of the benzanthrene series



Patented Aug 20, 1935 stares CONDENSATION PRODUCT OF THE BENZANTHRENE snares Carl Wulfi and Ernst Roell, Ludwigshafen-on- Rhine, Germany, assignor to General Aniline Works, inc, New York,

Delaware N. Y.', a corporation of No Drawing. Application January 22, 1934, Serial No. 707,849. In Germany January 25,

t The present invention relates tdcondensation productsof ithe'ibenzanthrene series and a process of producing same. g i

We have found that valuable condensation products are obtained by subjecting to a con-- densing treatment compounds capable of reactmg like benzanthrene, whereby mainly a condensation of-two molecules oiethe initial materials takes place. According to this process one fr'nolecula'r proportion of a compound capable of reacting like benzanthrene is condensedwith one molecular proportion of the same or a different compound capable of reacting like benzanthrene.

. Compounds capable of reacting like benzanthrene are benzanthrene itself, dihydrobenzanthrene (which is formedfor examplein the production of benzanthrene from alpha-benzylnaphthalene), jalpha-benzylnaphthalene (which first yields benzanthrene and/or dihydrobenzanthrene during the condensation) and benzanthrenes or dihydrobenzanthrenes substituted in the position marked X in the following formula KAI/W by substituents which are split off during the re- (which is usually called benzanthrone).

' b'e'nzanthrenetor the corresponding dihydro comvpounds; also two"m'olecular. proportions of 10- action, namely hydroxy groups or halogen atoms.

jlhe two molecules to be'condensed maybe equal v f-or 'diiferentfas is-described in detail in the following. 7 1 molecular proportion of benzanthrene may 'be reacted with '1 molecular proportion of benzanthrene or dihydrobenzanthrene or 10- .monochlorbenzanthrene (or lll-monochlordihydrobenzanthrene) or IO-dichlorbenzanthrene or 10 hydroxybenzanthrene (or 10hydroXydihydroi benzanth'rene) 01 -10"- dihydroxybenzanthrene 1 molecular proportion of -10-monochlorbenzanthrene may'xbe condensed with lmolecular proportion of {lo-monochlorbenzanthrene" or lfl-monohydroxy- 8 Claims. (c1; 260-168) t,

naphthalene and the condensation according to the present invention may be carried outi'n one single operation. f

Besides the said compounds other materials may be used, such as dinaphthy1methane, benzyl- 'anthracene, benzylphenanthrene, naphthylphenfanthrylmethane, benzobenzanthrene and the dc:- rivatives of these compounds substituted by halor gen, oxygen OH) and also alkyl derivatives of the compounds described.

The reaction products are hydrocarbons which probably contain two radicles of the initial material, for example two benzanthrene radicles which possibly are combined in the Iii-positions. Also if initial materials substituted in the lurposition, for example 10-chlorbenzanthrene, are employed, the final products are substantially free from such substituent, i. e. free from chlorine.

The statements concerning the possible or probable constitution of the final products are given to facilitate the understanding of the reaction but are not intended to restrict the subjectematter of the application.

' The condensing treatmentmay be efiected by heating the initial materials or by acting thereon with condensing agents, preferably at elevated temperature, the condensation conditions such as temperature and kind of thecondensing agent, being so energetic or the treatment carried on for so long that a condensation mainly takes place in which 2 molecules of the initial materialunite together. v i

If the reaction be effected by heating the initial materials (for example benzanthrene') or mixtures (for example of benzanthrene andbenzanthrone) alone/h gh temperatures, usually above 300 and even of" from 600 to 800" C., are often necessary. If the condensation be effected by treatment with condensing agents at elevated temperaturesgusuallytemperatures be1ow30Q C. are suitabIefl'As condensing agents may be'rnentionedfor example chemical condensingagents; such as sulphur,

selenium lead oxide, sodamid a'nd aluminium chloride, or catalystshaving a condensing action (which term includes dehydrogenating catalysts) such as difficultly reducible metal oxides, bleaching earths, as for exampletonsil of silica gel, or

phosphoric acid. a I c t The process may bencarried out the liquid or gas phase in the presence or absence of diluents with or without the employment of increased working conditionsnecessary in each case'may be suitable diluents are for example nitrogen, steam and carbon dioxide. l

5. While by heating benzylnaphthalene 'in the presenceof-a catalyst,benzanthrene or mixtures thereof with dihydrobenzanthrene are mainly ob-' tained, a dark-colored substancehaving a green fluorescence is obtained When'the heating is especiall retracted or when hi her, tern eratures 10 y p g .of lper cent of a black substance having a green fluorescence which may be employed directly or than those for thejsaid reaction aref-selectedor' when otherwise more energetic conditions a re em- .1 I ployed for example the period of reaction'is prolonged. The new product may be separated'from' 15 the unreacted parts by dissolution in xylene and precipitation with petroleum ether. The analysis and molecular weight of the substance pointto a compound which is 'formed from 2wmolecules 0f benzanthrene by union in the 10-positions by 20 means of a double linkage.

is obtained bycharging benzanthrene or dihydros Y threne' over th'e, said catalyst under 'fthe I sameworkin'g conditions.

; The same compound may also or tlieirirfiixtures'with oxidizing or dehydrogenating agentsjsuch as sulphur or. le'adoxide; the same result is'alsfo" achieved by? heating 1 molecular port 11 of benzanthrenewith 1 molecular pro- 39 'pbrtion' 'of"benzanthrone'at"about 3llO C., if de sired; while adding afcondensing agent, such as 'i hosphoric acid; This, condensation q i j 1 337 The carrie out "riot Only with benzanthrene benzanthrene," but" also with other hydro elected among, those enumerated above lce ,anm e corr'sporidi'n'g' oxygen derivatives. Th id s bs'tancefmay 'also' be-obtained; by

, ng lm'olecular 'proportiori'oi lO-dichlbrbn- 'ilzanthren'e with lf'moleciilar' proportion of nonm) chlprinatdlbenzanthrene"at about 1100? c. The

same 'substan'ce' mayfalso be obtained simply by I v I fine n'g I0 monochlorbenzanthrene1alone,if'desir'dlrith presence'of diluents, Y The; new substances are fsolid, "brown to" redwin crystalline powders melting in'the pure ateabo v e 250 Qj'whicliare Somme in'aromatic 'd aIb oIi S and "ini halbig e natd "aromatic 0r al p at c 'ydroc'arbbns and diflicultly soluble in jmeth alcohol, ethyl alcohol, beiifzine'and parafiin 7 Th "substances are distinguished by an exy coming; power and strong fluorvper centthereof still'havea marked fluorescence trati'on the "said substances" still give an inell 'do'lbiatlbn With sulphlllllalcld, and

(65' in order to to'themthef appearance of cera "tainnatural and commercialproducts; When so ,'treated, *such organicfsolvents show an intense orange'coloration' and'green fluo"rescence." 7

For the purpose of coloring benzines, lubricating so oils;andEtheIikeitisnot necessarytousethe pure 'products but the'unpurifled materials may be used f-as theyareobtain'ed ior exa'mple from the thermal :condensation;

.flhetyfollowingfexamples will, further .i1lustrate 75 :the nature of this inventiontbut.theinyegntion is The same-compound I also obtained by leading benzanthrene or dihydrobenzanthrene over thesaid catalystunder the r w p j same working conditions instead of benzylnaph- V I be obtained by 25 treating, benzanthrenefo'rf dihydrobenzanthrene monochlorbenzanthrene) separates out.

esce nc e'; sothats'ub'stances containing only 0.0001

sually'green colorg" Even 'in such slight con- 1s constitutes a characteristic coloration by not restricted to these examples. The parts are by weight.- I

' Example If 1 kilogram of alpha-benzylnaphthalene vapor 5 be led per hour over each liter. of, a catalyst consisting 'of magnesium oxideprovided. with a surface layer of graphiteiby leading thereover benzine vapors at 800 0.), at from 750 to 780C a product is obtained which consists 'to the extent 10 after purification by dissolution in arom atic hydrocarbons for coloring benzine. It consists probably of a condensation product of 2 molecules thalene. The yield in this case is better.

I h Example? I 100 parts {of a mixture of benzanthrene and dihydrobenzanthrenej (obtainable for example by ;the presence of diluent gases such as carbon di- "oxide' oi-Water vapor) are mixed with parts of elementary sulphur andheated to 280 C. The substance described in Example 1 is formedwith ;a strong evolution of hydrogen sulphide. By extracting the excess of sulphur or by purification, with solvents, the product may be readily obtained free from sulphur. V v 1 Instead ofsulphur, lead oxide may be employed.

Ex mple 3 '100 parts of the mixture of benzanthrene and dihydrobenzanthrene obtained as described at the top of Example 2 are dissolved in 200 parts of carbon tetrachloride, "70 parts of chlorine then being led in. The solution first becomes colored red-brown and then an, insoluble substance (10- The mixture obtained is bo iledunder a reflux condenser, and hydrochloric acid escapes in large amounts. Thezundissolved product, passes into solution and the latter ha's a strong darkgreen fluorescence. By filtration and distilling off the carbon tetrachloride fromthe filtrate, a residue I" is obtained which consists mainlypithe con- 'densation v product having a green fluorescence and is free from chlorine. V W

r'mmpz a I :1 1 so A mixture Orzo psrispgt mmhin andilizparts of 'benzanthrone".is heated' for 3 hours at about 320?; C. With thesplitting off of water. a

condensation productis formed whichhas an in- 55 tense green color andfluorescence; Ifacon'dens- 'ing agent, as for example tonsil or; phosphoric acid, be employed, the reaction. may be'carried out by heating at;about 250 C," 1

,100 parts or ei0ehydroxydihydrobenzanthrene (which is identical with the. compound called ihydroxy trimethylenephenanthrene) .are I heated with .50 parts oftonsilat between 2.0Qfand-25Q C.

by acting on benzanthrene with phosphorus Condensation with the splitting off of water occurs. Besides a little benzanthrene and dihydrobenzanthrene a substance is obtained which according to analysis is dibenzanthrene. By sublimation in the high-vacuum the compound may be purified. By recrystallization from toluene it is obtained in a crystalline form.

Example 6 50 parts of -dichlorbenzanthrene (obtainable pentachloride) and 40 parts of benzanthrene are heated in 500 parts of chlorbenzene at between 100 and 120 C. Hydrogenchloride is split off and a product is formed which according to I nets of thebenzanthrene series which comprises subjecting to a condensing treatment one molecular proportion of a compound selected from the group consisting of benzanthrene, dihydroben zanthrene, alpha-benzylnaphtha1ene," and benzanthrenes or dihydrobenzanthrenes substituted in the 10-position by up to two hydroxy groups.

or halo-gen atoms with one molecular proportion of a compound selected from the said group the reactants being so chosen that at most two halo- V ucts of the benzanthrene series which comprises subjecting to a condensing treatment at elevated temperatures one molecular proportion of a compound selected from the group consisting of vbenzanthrene, dihydrobenzanthrene, alpha-benzylnaphthalene, and benzanthrenes or dihydrobenzanthrenes substituted in the 10-position by tween 300 and 800 C. one molecular proportion of a compound selected from the group consisting of benzanthrene; dihydrobenzanthrene, al-

phaebenzylnaphthalene, and benzanthrenes or dihydrobenzanthrenes substituted in the 10-position by up to two hydroxy groups or halogen atoms with one molecular proportion of a compound selected from the said group the reactants being so chosen that at most two halogen atoms or hydroxy groups are contained in the reaction mixture.

4. A process of producing condensation products of the benzanthrene series which comprises subjecting benzanthrene to a condensing treatment at between 600 and 800 C. i

5. A process of producing condensation products of the benzanthrene series which comprises subjecting a mixtureof benzanthrene and benzanthrone to a' condensing treatment at about 320 C.

6. A process of producing condensation products of the benzanthrene series which comprises chlorinating a mixture of benzanthrene and dihydrobenzanthrene in carbon tetrachloride and subjecting the solution of chlorination product to condensation by heating to boiling.

7. Condensation products obtained by condensing a compound selected from the group consisting of benzanthrene, dihydrobenzanthrene, alpha-benzylnaphthalene, and benzanthrenes or dihydrobenzanthrenes substituted in the 10-position by up to two hydroxy groups orhalogen atoms with one molecular proportion of a compound selected from the said group the reactants being so chosen that at most two halogen atoms or hydroxy groups are contained in the reaction mixture, being from brown to brown-red powders, soluble in sulphuric acid to give a green colora-' tion, soluble in aromatic hydrocarbons and chlorinated aliphatic hydrocarbons, diiiicultly soluble in methyl and ethyl alcohol, benzine and'paraflin oil and imparting to the said solvents already in very low concentrations an intense orange coloration and green fluorescence.

8. Condensation products obtained by condensing a compound selected from the group consisting of benzanthrene, dihydrobenzanthrene, alpha-benzylnaphthalene, and benzanthrenes or dihydrobenzanthrenes substituted inthe 10position by up to two hydroxy groups or halogen atoms with one molecular proportion of a compound selected from the said group the reactants being so chosen that at most two halogen atoms or hydroxy groups are containedin the reaction mixture, containing probably 2 benzanthrene radicles per molecule being from brown to brownred powders, melting above 250 C., soluble in sulphuric acid to give a green coloration, soluble in aromatic hydrocarbons and chlorinated aliphatic hydrocarbons, -difiicultly soluble in methyl and ethyl alcohol, benzine and parafiin oil and imparting to the said solvents already in very low concentrations an intense orange coloration and green fluorescence.

CARL WULFF. ERNST ROELL. 

